Reactivity of [WCl6] with Ethers: A Joint Computational, Spectroscopic and Crystallographic Study
Reactivity of [WCl6] with Ethers: A Joint Computational, Spectroscopic and Crystallographic Study
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[WCl6] 与醚的反应性：联合计算、光谱和晶体学研究
DOI：
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发表时间：
2016
期刊：
影响因子：
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通讯作者：
S. Zacchini
中科院分区：
文献类型：
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作者：
M. Bortoluzzi;F. Marchetti;G. Pampaloni;S. Zacchini
在氯化溶剂中，[WCl_6]与一系列醚类化合物发生了反应，并用分析、光谱和密度泛函方法对其进行了表征。四氢吡喃（thp）或1，4-二氧六环与[WCl 6]的加成反应可生成WCl 6···L [L = thp（1a），1，4-二氧六环（1b）]，其可逆加成产物可在溶液中用核磁共振谱检测到。[WCl 6]与thp以1：2的摩尔比在氯仿中回流反应得到[WOCl 4（thp）]（2a），其以51%的产率分离。从[WCl 6]与过量二甲醚的反应中分离出[WOCl 4（OMe 2）]（2b）和[WOCl 3（OMe 2）2]（3a），产率分别为53%和18%。[WOCl 3（OEt 2）2]（3b）是唯一确定的由[WCl 6]和OEt 2（1：2摩尔比）反应产生的金属化合物。根据NMR研究，2a，B和3a，B中的氧化物配体是通过涉及一当量有机反应物的双C-O键断裂产生的。[WCl 6]与1，2-二乙氧基乙烷的1：1反应产生[WCl 5（κ1-OCH 2CH 2 OEt）]（4）和少量的[WCl 4（κ2-EtOCH 2CH 2 OEt）]（5）。以[WCl 6]和苯甲醚为原料，通过Csp 3-O键的选择性活化，合成了芳基氧化物[WCl 5（OPh）]（6），产率62%。[WCl 6]和二苯醚在1，2-二氯乙烷中的混合物的长时间加热导致WV络合物[WCl 5（OPh 2）]的分离（7）。2a和3a的分子结构经X-射线衍射确定。
The reactions of [WCl6] with a series of ethers have been performed in chlorinated solvent and elucidated by means of analytical, spectroscopic and DFT methods. The addition of tetrahydropyran (thp) or 1,4-dioxane to [WCl6] resulted in the reversible formation of the adducts WCl6···L [L = thp (1a), 1,4-dioxane (1b)], detected in solution by NMR spectroscopy. The reaction of [WCl6] with thp in a molar ratio of 1:2 in chloroform at reflux afforded [WOCl4(thp)] (2a), which was isolated in 51 % yield. [WOCl4(OMe2)] (2b) and [WOCl3(OMe2)2] (3a) were isolated in yields of 53 and 18 %, respectively, from the reaction of [WCl6] with an excess of dimethyl ether. [WOCl3(OEt2)2] (3b) was the only identified metal compound produced from the reaction of [WCl6] and OEt2 (1:2 molar ratio). According to NMR studies, the oxide ligand in 2a,b and 3a,b was generated by double C–O bond cleavage involving one equivalent of organic reactant. The 1:1 reaction of [WCl6] with 1,2-diethoxyethane led to [WCl5(κ1-OCH2CH2OEt)] (4) and a minor amount of [WCl4(κ2-EtOCH2CH2OEt)] (5). The aryl oxide compound [WCl5(OPh)] (6) was prepared in 62 % yield from the reaction of [WCl6] and anisole by selective Csp3–O bond activation. The prolonged heating of a mixture of [WCl6] and diphenyl ether in 1,2-dichloroethane led to the isolation of the WV complex [WCl5(OPh2)] (7). The molecular structures of 2a and 3a were ascertained by X-ray diffraction.
双(三甲基硅基)环己二烯的无盐还原剂介导W(VI)和W(IV)氯化物络合物的多电子还原
影响因子：
15
作者：
Tsurugi;Tanahashi;Nishiyama;Fegler;Mashima
通讯作者：
Mashima